Metallizable polyazo dyes from benzidine intermediates



Patented Mar. 11, 1947 UNITED STATES PATENT on? 2,417,306 ICE METALLIZABLE POLYAZO DYES FROM BENZIDINE INTERMEDIATES No Drawing. Application December 20, 1943, Serial No. 515,022. In Switzerland December 12 Claims. 1

It has been found that valuable copperable polyazo dyestuffs are obtained by combining tetrazotised 4 :4 -diamino-3 3 -dialkoxydiphenyl compounds, the alkoxy groups of which may also be substituted, in any suitable order of succession with l-molecule of an aminoazo dyestufi, which is obtainable by acid coupling of an o-carboxydiazonium compound of the benzene series, which may further be substituted in any way, with 2- amino--hydroxynaphthalene-'I-sulfonic acid and with 1 molecule of any coupling component containing at least one hydroxy group and being suitable for the manufacture of metallisable azo dyestuffs, which latter coupling component may be identical with the first one.

The first coupling of the said tetrazonium compounds with one molecule of the defined aminoazo dyestuff in order to form the so-called intermediate product, the disazoazo compound, is

readily carried out, while the further coupling with a second molecule of one of the said coupling components is much mor diflicult. The order of succession of the coupling may be chosen according to the coupling energy of the components. Components coupling diiiicultly are coupled with the diazo-azo-intermediate product in presence of pyridine. Besides the aminoazo dyestuffs already mentioned, which may be monoand disazo dyestufis, there may be used as coupling components for instance salicylic acid, m-cresotinic acid or l-naphthol-Z-carboxylic acid; moreover, for instance, the following naphthol compounds may also be used: p-naphthol, l-hydroxynaphthalene-4-sulfonic acid, Z-hydroxynaphthalened-sulfonic acid, 2 8-dihydroxynaphthalene-6-sulfonic acid, l-amino-8-hydroxynaphthalene-4- sulfonic acid, 1-amino-5-hydroxynaphthalene-"lsulfonic acid, 2-amino-8hydroxynaphthalene-6- sulfonic acid, 1-acetylamino-8-hydroxynaphthalene-Z-sulfonic acid, 1-acetyl-amino-8-hydroxynaphthalene-4-sulfonic acid, 1-phenylamino-8- hydroxynaphthalene-4-sulfonic acid, 1-benzoylamino 8 hydroxynaphthalene 4-sulfonic acid, 2-(4'- hydroxy- 3'- carboxyphenylamino) 5-hydroxy-naphthalene-7-sulfonic acid, 1-amino-8- hydroxynaphthalene-S:fi-disulfonic acid, l-amino-B-hydroxynaphthalene 2-:4 disulfonic acid and the like. For acid coupling with 2-amino-5- hydroxynaphthalene-7-sulfonic acid, there are suitable for instance the diazonium compounds of Z-aminobenzoic acid, 5-nitro-2-aminobenzoic acid, 4-methyl-2-amino-benzoic acid, 3- or 5- chloro-Z-amincbenzoic acid, 3:5-dich1oro-2-aminobenzoic acid, 5-acety1amino-2-amino-benzoic acid, 5-cyano-2-aminobenzoic acid, 2-(4'-amino- 3-carboxybenzenesulf)-aminobenzoic acid, 4'- hydroxy 4 aminoazobenzene -3:3-dicarboxylic acid and the like.

The new dyestuiis yield on cotton and regenerated cellulosic fibres navy-blue or violet-brown to black dyeings which, by after-treatment with copper salts according to known methods, become excellently fast to water and to washing without changing the shades in a noticeable manner.

The present invention will now be illustrated by way of the following examples, wherein the parts are by weight. Of course, the invention is not to be limited to the following examples.

Example 1 24.4 parts of 4:4'-diamino-3:3-dimethoxydiphenyl are tetrazotised, whereupon the solution of the tetrazonium salt is added at 0-2 C. to a solution of 86.4 parts of the monoazo dyestuff obtainable according to known methods in an acid solution from diazotised 5-nitro-2-aminobenz oic acid and 2-amino-5-hydroxynaphthalene-'7-sulionic acid in 600 parts of water and in the presence of 314 parts of pyridine and 15 parts of ammonia. After having completed the coupling by stirring for several hours at room temperature the dyestuff is precipitated at 40 C. by means of sodium chloride, then filtered off and dried.

The new tetrakisazo dyestuff being a dark bronzy powder dissolves in water with a blue coloration and in concentrated sulfuric acid with a dirty violet-blue coloration and dyes cellulosic fibres in navy-blue shades. By a subsequent coppering the dyeing becomes somewhat deepened; it possesses valuable fastness properties in the moist state.

If in this example 5-m'tro-2-aminobenzoic acid is replaced by 2-amino-benzoic acid, 4-methyl- Z-aminobenzoic acid, 3-chloro-2-aminobenzoic acid, 3:6-dichloro-2-amino-benzoic acid, 5-acetylamino-Z-aminobenzoic acid, 5-cyano-2-aminobenzoic acid, 2 -(4-amino 3- carboxybenzenesulf)aminobenzoic acid, dyestuffs with similar properties are obtained.

Example 2 v 24.4 parts of 4:4'-diamino-3:3'-dimethoxydiphenyl are tetrazotised, whereupon the tetrazo compound thus obtained is added to a solution of 84.3 parts of the monoazo dyestuff obtainable by coupling diazotised 4-chloro-2aminobenzoic acid and .2-amino -5- hydroxynaphthalen'e-'7-sulfonic acid in 600 parts of water, 314parts of pyridine and 15 parts of ammonia; After a stirring for several hours at room temperature the coupling is complete, whereupon the dyestuff thus obtained is salted out at 40 C. by means of sodium chloride, then filtered off and dried.

The new dyestuff constitutes a dark bronzy powder. It is soluble in water with a blue coloration and in concentrated sulfuric acid with a dirty violet-blue coloration and dyes .cellulosic fibres in navy-blue shades becoming somewhat darker, when subsequently coppered, and possessing very good fastness properties to light and in the moist state.

The propertiesof the dyestuff remain the same,

if instead .of 4.:4-diamino-3:3'-dirnethoxydi phenyl there is used for example 4:4-diamino-,

33.7 parts of the monoazo dyestuff obtainable from diazotised 2-aminobenzoic acid and 2-amino-5- hydroxynaphthalene-7-sulfonic acid, the coupling taking place rapidly. After completion of the dyestufi formation the solution cooled down to 5-" C. is coupled at this temperature with a solution of 43.2 parts of the monoazo dyestuif obtainable from diazotised -nitro-2-aminobenzoic acid and 2-amino-5-hydroxynaphthalene-"I- sulfonic acid in 300 parts of water, 250 parts of pyridine and 8 parts of ammonia. After a stirring for several hours .at. room temperature also the second coupling is complete. After being warmed up to 40 C. the dyestuif is salted out by means of sodium chloride, filmred oiT and dried.

The new dyestufi is a dark bronzy powder which dissolves in water with a blue coloration and in concentrated sulfuric acid with a dirty violet-blue coloration. It dyes cellulosic fibres in navy-blue shades becoming somewhat darker,

' when subsequently coppered, and having improved fastness properties to light and in the moist state.

Of course, by working in the manner described in this example, any other combinations may be prepared, if either the Z-aminobenzoic acid is replaced by any other compound mentioned at the end of Example 1 or if another dialkoxydiaminodiphenyl compound is used.

Example 4 24.4 parts of 4:4-diamino-3:3-dimethoxydiphenyl are tetrazotised in the usual manner and combined with 15.3 parts of salicylic acid and 30 parts of sodium carbonate. As soon as the formation of the intermediate product is completed, coupling is effected in the presence of 150 parts of pyridine and parts of sodium carbonate with the monoazo dyestufi which is' obtainable by acid coupling of 13.7 parts of di-' off and'dried. It constitutes a dark powder dissolving in water with a red-violet coloration and in concentrated sulfuric acid with a blue coloration. It dyes cellulosic fibres, after having subsequently been treated with copper sulfate, in

violet-brown shades of very good fastness properties in the moist state.

When, in this example] the 2-aminobenzoic acid is replaced by 4-methyl-2-aminobenz'oic acid, 4-ch1oro-2-aminobenzoic acid or 5-acetylamino-Z-aminobenzoic acid, dyestuffs with similar properties are obtained.

1 side in a soda-alkaline solution with 17 parts of m-cresotinic acid; The diazoazo compound is allowed to flow into a solution of 43.2 parts of 4 the monoazo dyestuff obtainable byacid coupling of diazotised 5-nitro-2-aminobenzoic acid with 2 amino-5-hydroxynaphthalene-7-su1fonic acid in 300 parts of water, parts of pyridine and 20-parts of sodium carbonate. After the complete coupling the trisazo dyestuff is salted out,

powder dissolving in water with a violet coloration and dyeing cellulosic fibres in black shades, as farasthe fibreshavesubsequently been coppered.

Example 6 24.4 parts of 4:4-diamino-3:3-dimethoxydiphenyl are tetrazotised in a hydrochloric acid solution with 13.8 parts of sodium nitrite and combined, in the presence of an excess of sodium carbonate, with a solution of 43.2 parts of the monoazo dyestuff which has been prepared by coupling in an acid medium diazotised 5-nitro- Z-aminobenzoic acid with 2-amino-5-hydroxynaphthalene-'Lsulfonic acid. When the intermediate compound has been formed, it is treated with an aqueous solution of 18.8 parts of 1- hydroxy-Z-naphthalene carboxylic acid, 20 parts of sodium carbonate and 150 parts of pyridine. After several hours the second coupling is. also complete. The dyestuiiis precipitated by means of sodiumchloride, then filtered off and dried.

The new dyestuff is a dark powder which dissolves in water with a violet coloration and in concentrated sulfuric acid with a blue coloration. The after-coppered, dyeings on cellulosic fibres are black and .possess'good fastness properties to washing and to water.

A dyestuff with similar properties is obtained, when using 4:4'-diamino 3:3 dicarboxy-methoxydiphenyl instead of 4:4'-diamino-3:3-dimethoxydiphenyl.

Example. 7

The diazoazo compound made according .to EXample'4 from 24.4 parts of 4:4-diamino'-3:3'-

dimethoxy diphenyl and, 15.3 parts of salicylic acid is combined in, the-presence of 150 parts of pyridine and 15 partsof. sodium carbonatewith 65.1 parts of the dyestuff which has been ob tained by acid coupling diazotised 4-hydroxy- 4- coloration.

v v Example 8' 24.4 parts of 4':4,'-diamino-3z3 -dimethoxydiphenyl are tetrazotised ina hydrochloric acid solution with 13.8 parts of sodium nitrite and combined, in the presence of excess sodium carbonate, with a solution of 42.1 parts of. the monoazo dyestufl obtainable by coupling in an acid medium diazotised 4-chloro-2-aminobenzoic acid with 2-amino-5-hydroXynaphthalene-7-sulfonic acid. After the formation of the intermediate Example 10 24.4 parts of 4:4J-diamino-3:3-dimethoxydiphenyl are tetrazotised and combined, in the presence of excess sodium carbonate, with a solucompound the Same is treated with an aqueous tion of 38.7 parts of the monoazo dyestufi obtainsolution of 22.4 parts of 1-hydroxynaphthalene-4- able by coupling in an acid medium sulfonic acid and 20 parts of sodium carbonate. benzoic acid with 2 amino 5 hydroxynaphtha After some hours the second .coupling 18 lene-7-sulfonic acid. As soon as the intermediplete. The dyestuff is then preclpitated by means ate compound is formed an aqueous Solution of of sodium chloride, filtered and dried. 10 319 parts of l amino s hydroxynaphthalene The new dyestufi is a dark bronzy Powder 2:4-disulfonic acid, 20 parts of sodium carbonate solving in water with a blue coloration and in and 150 parts of pyridine is allowed to flow into concentrated sulfuric acid with a greenish'blue the intermediate product. After some hours the coloration and dyeing cellulosic fibres in reddish- Second coupling has fi i hed The d estuff is navy'blue shadesafter'coppering dyeings now precipitated by means of sodium chloride, of very valuable iastness properties in the moist filtered off and fined state are obtamed' The new dyestufi" constitutes a dark bronzy Example 9 powder which is soluble in water with a blue coloration and in concentrated sulfuric acid with 24.4 parts of 41 t -d1am1no-3:3 -dlmethoxyd a green coloration and which dyes cellulosic fiphenyl are tetrazotised and coupled on one half bras in greenish navy blue Shades w afield side in a soda-alkaline solution with 43.2 parts coppered the dyeings Show Very Valuable fast of the monoazo dyestuff obtainable by acid coumess properties in the moist Sham pling of diazotised -nitro-z-aminobenzoic acid with 2-amino-S-hydroxynaphthalene-7-sulfonic Example 11 acid. Then an aqueous solution of 22.4 parts of 24,4 parts of 4;4'-di in0-3;3-dimethoxydiyd y ap a -fi-s acid, 20 parts phenyl are tetrazotised and coupled in a soda- Of S d u Carbonate and Parts Of py is alkaline solution with 37.5 parts of 2- (4'-hydroxycaused to flow into the obtained intermediate 3' carboxyphenyiamino);5 hydroxynaphthalene p Th plin h v b n c mpl ted by 3D v-sulfonic acid. Then an aqueous solution of 43.2 a Stirring f0? several hours at room p a parts of the monoazo dyestuff obtainable by couthe dYeStuTf is p p tated at C. by means of pling diazotised S-nitro-Z-aminobenzoic acid Sodium chloride, then filtered O and dri d. with 2-arnino-B-hydroxynaphthalene-7-sulfonic Th n dyeStll a dark bronzy powder, disacid in the presence of 20 parts of sodium carsolves in Water and in concentrated sulfuric acid i t d 150 parts of pyridine i caused t flow giving a blue coloration and dyes cellulosic fibres into the intermediate product. After a stirring in redd s y- Shades- When Subsequently for several hours at room temperature the finpp the yei gs DOSSBSS ood fastness DIOD- ished trisazo dyestuff is precipitated by means of erties in the moist state. sodium chloride, filtered and dried.

If, in this example, the monoazo dyestuif from 3 The new dyestuff is a dark powder which is 5-nitro-2-amin0benz0ic a id and 2-am n -hysoluble in water with a violetish-blue coloration droxynaphthalene-'l-sulfonic acid is replaced y and in concentrated sulfuric acid with a blue t disaZO dyeslillfi Obtainable from diELZOtiSEd 4' coloration; it dyes cellulosic fibres, when subsehydroxy l-aminoazobenzene 3:3 dicarboxylic quently coppered, in reddish-navy-blue shades of acid and 2-amino-5-hydroxynaphthalene-7-sul- 455 good fastness properties in the moist state. ionic acid, a dyestuff of similar properties is ob- Further combinations according to this inventained. tion are enumerated in the following table:

Table Shade of the Tetrazo compound figd'i gii ghit i -i ifiloi'fi gdfi Naphtholsulfonic acid compound gg g and diazotised ga;

4:4-diamino-3:3-dimethoxydipheny1. 5-nitro-2-amino-benzoic aciduui l-amlno8:hydroxynaphthalcne-2zi-disnl- Navy-blue.

4-methyl-2-aminobenzoic acid. Z-hfiiifoifiaphthalene-fi-sulfonic acid Do. Z-aminobenzoic acid 1- I a iillliilgi8d-hydroxynaphthalene-4-sul- Do. 5-cli1oro 2-aminobenZoic acid l-phenylanlino S-hydroxynaphthalen- Do.

. i-sulfonic acid 5-nitro-2-aminobenzoic acid 1-amino-8-hydroxynaphthalcnc3:fi-disul- Grcenl'sh-navyionic acid. blue. Do 4'41ydroxy-l-aminoazobcnzenc-3z3-dicar- 1-hydroxynaphthalene-i-sulfonic aci l Navy-blue.

boxylic acid. Do l-amino-5-hydroxynaphthalcnc-7-sulfon- 5-nitro-2-aminobenzoic acid .do Q.

2-aminobenzoic acid 1c acid.

Greenish-navyblue.

2amimgS-hydroxynaphthalene-fi-sulfon- Navy-blue.

l-acetylamino-fl-hydroxynaphthalene-2- Reddish-navysulfonic acid. blue l-benzoylamino-B-hydroxynaphthalcne- Greenish-navy bl e 4-sulf0nic acid. u dchloro-Z-aminobenzoic acid l-amino-8-hydroxynaphthalene-326-di- Navy-blue.

. sulfonic acid. 5-nitro-2raminobenzoic acid l-amin gi-hydroxynaphthalcne-l-sulion- Glaenish-navy- 10 am ue. .do l-acetylamino-l-hydroxynaphthalenel- Rcddish-navysulfonic acid. blue. do l-phenylamino-Bf-hydroxynaphthalcncl- Do.

snllonic acid. do 1-benzoylamino-8-hydroxynaphthalcne- Reddish-navy- 4-sulfonic acid. ue. asulfo-Z-aminobenZoic acid Do.

Z-hydroxynapbthalene What we claim is:- 1. Process for the manufacture of polyazo dyestuffs capable of being coppered, of the general formula which comprises coupling a tetrazotised amine .of the formula wherein X means a member of the group consisting of CH3, C2H5 and CH2COOH, with one molecule of a coupling component H-A1 and with one molecule of a coupling component H-A2, HA1 being a monoazo dyestufi of the general formula R meaning at least one member ofrthe group con sisting of H, C1, CH3, N02, CN, NH.COCH3 and .7

--SOzNH.CsH4.COOH(1:2), and H--A2 being ah member of the group consisting of'H-A1,'sa1i'- cylic acid, m-cresotinic acid, l-hydroxynaph thalene-2-carboxylic acid, ,B-naphthol and hidroxynaphthalene sulfonic acid compounds ca V pable of being coupled in o-position to the hy droxy group.

' 2. Process for the manufacture ofpolyaz o dye-' stuffs capable of being coppered, of the general formula N=NA1 OCHav V which comprises coupling tetrazotised 4:4'-di-" amino-3:3'-dimethoxydiphenyl With one mole cule of a coupling component H--A1 andwith one molecule ofacoupling component H- A2, H-A1 'being a monoazo dyestuff'of the general formula C|OOH r Q R 11035 NHa pable of being coupled in o position to the hy-V droxy group. i

3. Process for the manufacture of polyazo dyestuifs capable of being coppered, of the general formula I. I COOH NHi OCH3

OCHs

which comprises coupling tetrazotised elz4'-diamino-3:3-dirnethoxydiphenyl with one mole-7 culeof the monoazo dyestuif obtained by coupling diazotised 5-nitroanthranilic acid with Z-amino- 5-hydroxynaphthalene-7-sulfonic acid and with one molecule of the coupling compound .l-L-Az, HA2 being a member of the group consisting of the mon'oazo' dyestuff of the generarformula V v I 1 7 V V p R 1103s 7 NH2 salicylic acid, mcresotinic acid, l-hydroxynaphthalene-Z-carboxylic acid, fl-naphthol and hydroxynaphthalene sulfonic acid compounds ca-- pable of being coupled in o-position to the hydroxy group, R meaning at least one member of the group consisting of l-I,.Cl,.. CH3, N02, ON, 7

7 l. Process for the manufacture of a polyazo dyestuif, capable of being coppered, which comprises coupling tetrazotised 4:4'-diamino-3:3-

dimethoxydiphenyl with two molecules 'of the monoazo dyestuff obtained by acid )coupling' diazotised 5-nitroanthranilic.acidwithfiaminm' 5-hyclroxynaphthalene 7-sulfonic acid. 3

5; Process for the manufacture of -a'polyazo1 N=NAa wherein X means a memberof the group consisting of -CH3, -C2H5 and CH2.COOH, A1 means a radical of coupled compounds of the formula coon HOaS

R meaning at least one member of the group consisting of H, Cl, CH3, N02, CN, NH.COCH3 and -SO2NI-I.CsH4.COOI-I(1:2), and A2 means a radical of compounds of the group consisting of H-A1, salicylic acid, m-cresotinic acid, lhydroxynaphthalene-2-carboxy1ic acid, fl-naphthol and hydroxynaphthalene sulfonic acid compounds capable of being coupled in o-position to the hydroxy group, being dark powders, dissolving in water with a blue to violet coloration and dyeing cellulosic fibres, when after-coppered, in blue to black shades of excellent fastness properties.

8. The polyazo dyestuffs, capable of being coppered, corresponding in the free state to the' general formula 1TI=NA| OCH:

wherein A1 means a radical of coupled compounds of the formula HOaS NH2 R meaning at least one member of a group consisting of H, Cl, CH3, N02, CN, NI-I.C0CH3 and SO2.NII.C6H4.COOH(O), and A2 means a radical of compounds of the group consisting of HA1, salicylic acid, m-cresotinic acid, 1-hydroxynaphthalene-2-'carboxylio acid, rp -naphthol and hydroxynaphthalene sulfonic acid compounds capable of being coupled in o-position to the hydroxy group; being dark powders, dissolving in water with a blue to violet coloration and dyeing cellulosic fibres, when after-coppered, in blue to black shades of excellent fastness prop erties.

9. The polyazo dyestuffs, capable of being cop- .pered, corresponding in the free state to the general formula wherein A2 means a radical of compounds of the group consisting of the monoazo dyestuff of the eneral formula salicylic acid, m-cresotinic acid, l-hydroxynaphthalene-Z-carboxylic acid, fl-naphthol and hydroxynaphthalene sulfonic acid compounds capable of being coupled in o-position to the hydroxy group, R meaning at least one member of the groups consisting of H, Cl, CH3, N02, CN, --NHCOCH3 and -SO2NH.C6H4.COOH(1Z2), being dark powders, dissolving in water with a blue to violet coloration and dyeing cellulosic fibres, when after-coppered, in blue to black shades of excellent fastness properties.

10. The polyazo dyestufl, capable of being cop- :11 pered, corresponding in the free state to the formula being a dark powder, dissolving in water with a blue coloration-and dyeing cellulosic fibres, when after-coppered, in blue shades of excellent fastness properties.

11. The polyazo dyestufi, capable of being coppered, corresponding, in the free state to the formula COO'H 1'2 being a dark powder, dissolving in water with a violet coloration and dyeing cellulosic fibres, when after-coppered, in black shades of,.excel1ent fastness properties.

'12. The polyazo dyestufi, capable of being coppered, corresponding in the free state to the being a dark powder, dissolving in water with a blue coloration and dyeing cellulosic fibres, when after-coppered, in blue shades of excellent fastness properties.

ADOLF KREBSER. WERNER BOSSARD. PETER HINDERMANN.

REFERENCES CITED The following references are of record in the file of this pat nt:

UNITED STATES PATENTS Number Name Date 1,282,355 Anderwert-et al Oct. 22, 1918 1,901,387 Wiedemann et a1. Mar. 14, 1933 2,277,262 Stein et al Mar. 24, 1942 

